2216-69-5Relevant articles and documents
Proton-Induced Electro-Transfer Reaction from Triplet Methoxynaphthalenes to Benzophenone via Triplet Exciplex
Yamaji, Minoru,Sekiguchi, Tetuhiro,Hoshino, Mikio,Shizuka, Haruo
, p. 9353 - 9359 (1992)
A laser flash photolysis study at 355 nm has been carried out on acetonitrile-water (4:1 v/v) mixtures of the methoxynaphthalene-benzophenone-H2SO4 system.It is found that the proton-assisted photoionization reaction of triplet 1- and 2-methoxynaphthalene (ROMe) produced by triplet sensitization of benzophenone (BP) effectively occurs to produce the corresponding methoxynaphthalene cation radical (ROMe(1+.)) and benzophenone ketyl radical (>C(.)OH).The triplet energy-transfer reaction from triplet benzophenone (3BP*) to ROMe takes place as the primary event to produce triplet methoxynaphthalene (3ROMe*).The 1:1 triplet exciplex 3(ROMe...>CO)* having a weak charge-transfer structure is readily formed between 3ROMe* and BP with the equilibrium constants K1 (10.1 M-1 for 1ROMe; 4.0 M-1 for 2ROMe at 290 K).In the presence of protons, the triplet protonated exciplex 3(ROMe...>C(1+)OH)* is also produced by protonation to 3(ROMe...>CO)*.Subsequently, the intraexciplex electron-transfer reaction in 3(ROMe...>C(1+)OH)* takes place effectively, resulting in the formation of ROMe(1+.) and >C(.)OH.The presence of protons in the ROMe-BP system assists the photoionization of ROMe with the much lower energy (triplet energy of ROMe) than its ionization potential.The reaction mechanism is discussed in detail.
A Mild Heteroatom (O -, N -, and S -) Methylation Protocol Using Trimethyl Phosphate (TMP)-Ca(OH) 2Combination
Tang, Yu,Yu, Biao
, (2022/03/27)
A mild heteroatom methylation protocol using trimethyl phosphate (TMP)-Ca(OH)2combination has been developed, which proceeds in DMF, or water, or under neat conditions, at 80 °C or at room temperature. A series of O-, N-, and S-nucleophiles, including phenols, sulfonamides, N-heterocycles, such as 9H-carbazole, indole derivatives, and 1,8-naphthalimide, and aryl/alkyl thiols, are suitable substrates for this protocol. The high efficiency, operational simplicity, scalability, cost-efficiency, and environmentally friendly nature of this protocol make it an attractive alternative to the conventional base-promoted heteroatom methylation procedures.
Direct Hydrodecarboxylation of Aliphatic Carboxylic Acids: Metal- and Light-Free
Burns, David J.,Lee, Ai-Lan,McLean, Euan B.,Mooney, David T.
supporting information, p. 686 - 691 (2022/01/28)
A mild and inexpensive method for direct hydrodecarboxylation of aliphatic carboxylic acids has been developed. The reaction does not require metals, light, or catalysts, rendering the protocol operationally simple, easy to scale, and more sustainable. Crucially, no additional H atom source is required in most cases, while a broad substrate scope and functional group tolerance are observed.
Preparation method of naphthalene ring C marked α .
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Paragraph 0046-0048; 0056-0058; 0066-0068, (2021/10/05)
The invention discloses C labeled α - naphthalene acetic acid preparation method and belongs to the field of radioisotope C labeled compounds. C-labeled α - naphthylacetic acid preparation method, C radioisotope labeling is introduced on a naphthalene ring structure α -naphthol acid, C labeling site is in α-position. The method has the advantages that the reaction raw materials are easily available, the synthesis steps are high in yield, the total yield is more 60%, C marker isotopes are less in use amount, and waste is generated. The marker site α-position on the naphthalene ring is less likely to be metabolized compared to C-labeled branched acetic acid, and the synthesized C-labeled compound provides a better study of α -naphthoic acid in the environment.
A highly stable all-in-one photocatalyst for aryl etherification: The NiIIembedded covalent organic framework
Chen, Hao,Dong, Wenbo,Hu, Jianxiang,Rao, Li,Wang, Pei,Wang, Shengyao,Xiang, Yonggang,Yang, Yi
, p. 5797 - 5805 (2021/08/23)
The efficient conversion of aryl bromides to the corresponding aryl alkyl ethers by dual nickel/photocatalysis has seen great progress, but difficulties of recycling the photosensitizer or nickel complexes cause problems of sustainability. Here, we report the design of a novel, highly stable vinyl bridge 2D covalent organic framework (COF) containing Ni, which combines the role of photosensitizer and reactive site. The as-prepared sp2c-COFdpy-Ni acts as an efficient heterogeneous photocatalyst for C-O cross coupling. The sp2c-COFdpy-Ni can be completely recovered and used repeatedly without loss of activity, overcoming the limitations of the prior methods. Preliminary studies reveal that strong interlayer electron transfer may facilitate the generation of the proposed intermediate sp2c-COFdpy-NiI in a bimolecular and self-sustained manner. This all-in-one heterogeneous photocatalyst exhibits good compatibility of substrates and tolerance of functional groups. The successful attempt to expand the 2D COFs with this new catalyst into photocatalytic organic transformation opens an avenue for photoredox/transition metal mediated coupling reactions.
Methylation with Dimethyl Carbonate/Dimethyl Sulfide Mixtures: An Integrated Process without Addition of Acid/Base and Formation of Residual Salts
Chan, Bun,Lui, Matthew Y.,Lui, Yuen Wai
, (2022/01/08)
Dimethyl sulfide, a major byproduct of the Kraft pulping process, was used as an inexpensive and sustainable catalyst/co-reagent (methyl donor) for various methylations with dimethyl carbonate (as both reagent and solvent), which afforded excellent yields of O-methylated phenols and benzoic acids, and mono-C-methylated arylacetonitriles. Furthermore, these products could be isolated using a remarkably straightforward workup and purification procedure, realized by dimethyl sulfide‘s neutral and distillable nature and the absence of residual salts. The likely mechanisms of these methylations were elucidated using experimental and theoretical methods, which revealed that the key step involves the generation of a highly reactive trimethylsulfonium methylcarbonate intermediate. The phenol methylation process represents a rare example of a Williamson-type reaction that occurs without the addition of a Br?nsted base.
Catalytic SNAr Hydroxylation and Alkoxylation of Aryl Fluorides
Kang, Qi-Kai,Li, Ke,Li, Yuntong,Lin, Yunzhi,Shi, Hang,Xu, Lun
supporting information, p. 20391 - 20399 (2021/08/13)
Nucleophilic aromatic substitution (SNAr) is a powerful strategy for incorporating a heteroatom into an aromatic ring by displacement of a leaving group with a nucleophile, but this method is limited to electron-deficient arenes. We have now established a reliable method for accessing phenols and phenyl alkyl ethers via catalytic SNAr reactions. The method is applicable to a broad array of electron-rich and neutral aryl fluorides, which are inert under classical SNAr conditions. Although the mechanism of SNAr reactions involving metal arene complexes is hypothesized to involve a stepwise pathway (addition followed by elimination), experimental data that support this hypothesis is still under exploration. Mechanistic studies and DFT calculations suggest either a stepwise or stepwise-like energy profile. Notably, we isolated a rhodium η5-cyclohexadienyl complex intermediate with an sp3-hybridized carbon bearing both a nucleophile and a leaving group.
Design, synthesis, and anticancer evaluation of benzophenone derivatives bearing naphthalene moiety as novel tubulin polymerization inhibitors
Wang, Guangcheng,Liu, Wenjing,Tang, Juan,Ma, Xue,Gong, Zipeng,Huang, Yong,Li, Yongjun,Peng, Zhiyun
, (2020/09/15)
A series of benzophenone derivatives bearing naphthalene moiety were designed, synthesized, characterized by 1H NMR, 13C NMR, and HRMS and evaluated for their antiproliferative activity against human breast cancer cell line (MCF-7). Most of the tested derivatives showed good to moderate cytotoxicity against MCF-7 cell line. Among them, compound 4u (IC50 = 1.47 ± 0.14 μM) was found to be the most active compound, which is more active than the standard drug cisplatin (IC50 = 15.24 ± 1.27 μM). In vitro tubulin polymerization inhibition assay, EBI competition assay, cell cycle analysis, and cell apoptosis assay identified that compound 4u was a new tubulin polymerization inhibitor by targeting the colchicine binding site. Besides, molecular docking study showed that compound 4u has high binding affinities with the colchicine binding site of tubulin through hydrogen bond, cation-π, and hydrophobic interaction.
Menbutone intermediate synthesis method
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Paragraph 0009-0011, (2019/05/02)
The invention discloses a menbutone intermediate synthesis method, which comprises: pouring 1-naphthol, tetrabutylammonium bromide and sodium carbonate into dimethyl carbonate, heating to achieve a refluxing state, carrying out a complete reaction, carrying out pressure reducing distillation to remove the excess dimethyl carbonate, cooling to a room temperature, adding water, adding an acid in a dropwise manner to adjust the pH value to 3-4, extracting with dichloromethane, and reducing the pressure to remove the solvent so as to obtain the menbutone intermediate 1-methoxy naphthalene. According to the present invention, the method has characteristics of simple operation, high yield, no toxicity and no harm, greatly reduces the harm to operators and the environment, and is suitable for enterprise production.
Corey-Chaykovsky Cyclopropanation of Nitronaphthalenes: Access to Benzonorcaradienes and Related Systems
Antoniak, Damian,Barbasiewicz, Micha?
supporting information, p. 9320 - 9325 (2019/11/19)
Nitronaphthalene derivatives react as Michael acceptors in the Corey-Chaykovsky reaction with alkyl phenyl selenones and alkyl diphenyl sulfonium salts. Mechanistic studies reveal that sterically demanding substituents at the carbanionic center favor formation of cyclopropanes and suppress competitive β-elimination to the alkylated products. The transformation, demonstrated also on heterocyclic nitroquinoline and nitroindazolines, is an example of transition metal-free dearomatization method.
